JPH0472071A - Electroless tin and tin-lead alloy plating bath and plating method - Google Patents
Electroless tin and tin-lead alloy plating bath and plating methodInfo
- Publication number
- JPH0472071A JPH0472071A JP18448890A JP18448890A JPH0472071A JP H0472071 A JPH0472071 A JP H0472071A JP 18448890 A JP18448890 A JP 18448890A JP 18448890 A JP18448890 A JP 18448890A JP H0472071 A JPH0472071 A JP H0472071A
- Authority
- JP
- Japan
- Prior art keywords
- tin
- acid
- plating
- electroless
- bath
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000007747 plating Methods 0.000 title claims abstract description 65
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910001128 Sn alloy Inorganic materials 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 8
- 229910001174 tin-lead alloy Inorganic materials 0.000 title abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 36
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001432 tin ion Inorganic materials 0.000 claims abstract description 13
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 150000007513 acids Chemical class 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000002253 acid Substances 0.000 abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 239000010949 copper Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 229910000881 Cu alloy Inorganic materials 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- 238000007772 electroless plating Methods 0.000 abstract description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 2
- 239000010452 phosphate Substances 0.000 abstract 2
- 238000009713 electroplating Methods 0.000 abstract 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 abstract 1
- 235000011007 phosphoric acid Nutrition 0.000 description 14
- 230000000873 masking effect Effects 0.000 description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 5
- 150000003460 sulfonic acids Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- YCELPWGPXSJYMB-OWOJBTEDSA-N (e)-2-sulfobut-2-enedioic acid Chemical compound OC(=O)\C=C(/C(O)=O)S(O)(=O)=O YCELPWGPXSJYMB-OWOJBTEDSA-N 0.000 description 1
- YCELPWGPXSJYMB-UPHRSURJSA-N (z)-2-sulfobut-2-enedioic acid Chemical compound OC(=O)\C=C(\C(O)=O)S(O)(=O)=O YCELPWGPXSJYMB-UPHRSURJSA-N 0.000 description 1
- MCXZBEZHTYZNRE-UHFFFAOYSA-N 1-chloropropane-1-sulfonic acid Chemical compound CCC(Cl)S(O)(=O)=O MCXZBEZHTYZNRE-UHFFFAOYSA-N 0.000 description 1
- DIZBQMTZXOUFTD-UHFFFAOYSA-N 2-(furan-2-yl)-3h-benzimidazole-5-carboxylic acid Chemical compound N1C2=CC(C(=O)O)=CC=C2N=C1C1=CC=CO1 DIZBQMTZXOUFTD-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- NSRGOAGKXKNHQX-UHFFFAOYSA-N 2-hydroxybutane-1-sulfonic acid Chemical compound CCC(O)CS(O)(=O)=O NSRGOAGKXKNHQX-UHFFFAOYSA-N 0.000 description 1
- RIYJUQDMHMUBMK-UHFFFAOYSA-N 2-hydroxypentane-1-sulfonic acid Chemical compound CCCC(O)CS(O)(=O)=O RIYJUQDMHMUBMK-UHFFFAOYSA-N 0.000 description 1
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 1
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-UHFFFAOYSA-N 0.000 description 1
- WBGKAOURNYRYBT-UHFFFAOYSA-N 2-sulfopropanoic acid Chemical compound OC(=O)C(C)S(O)(=O)=O WBGKAOURNYRYBT-UHFFFAOYSA-N 0.000 description 1
- OURSFPZPOXNNKX-UHFFFAOYSA-N 3-sulfopropanoic acid Chemical compound OC(=O)CCS(O)(=O)=O OURSFPZPOXNNKX-UHFFFAOYSA-N 0.000 description 1
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- BRXCDHOLJPJLLT-UHFFFAOYSA-N butane-2-sulfonic acid Chemical compound CCC(C)S(O)(=O)=O BRXCDHOLJPJLLT-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 210000000496 pancreas Anatomy 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- RJQRCOMHVBLQIH-UHFFFAOYSA-M pentane-1-sulfonate Chemical compound CCCCCS([O-])(=O)=O RJQRCOMHVBLQIH-UHFFFAOYSA-M 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- HNDXKIMMSFCCFW-UHFFFAOYSA-N propane-2-sulphonic acid Chemical compound CC(C)S(O)(=O)=O HNDXKIMMSFCCFW-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- AGGIJOLULBJGTQ-UHFFFAOYSA-N sulfoacetic acid Chemical compound OC(=O)CS(O)(=O)=O AGGIJOLULBJGTQ-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、電子部品における銅回路を形成するためのエ
ツチングレジスト、半田付けを行う場合などに好適に用
いられる酸性の無電解錫、無電解錫・鉛合金めっき浴及
び無電解錫、無電解錫・鉛合金めっき方法に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to etching resists for forming copper circuits in electronic components, acidic electroless tin suitable for soldering, etc. This invention relates to a tin/lead alloy plating bath, electroless tin, and electroless tin/lead alloy plating method.
〔従来の技術及び発明が解決しようとする課題〕従来よ
り、電子部品等に半田付は性などの点から無電解錫めっ
きを施すことが行われているが、この場合電子部品等の
めっき不要箇所をマスキングし、必要箇所のみをめっき
する部分めっきがなされることが多い。かかる部分めっ
きを行う場合、特に電子部品のめっきにおいてはマスキ
ング精度が強く要求され、これに対応して種々のマスキ
ング剤、マスキング方法が開発されているが、一般にマ
スキング剤はアルカリ性に弱く、アルカリ性のめっき浴
でめっきを行うとマスキング膵が剥離を起こすことがあ
り、また電子部品等の素材が多様化していることにより
、耐アルカリ性の悪い素材も増え、このためかかる部分
めっき用のめつき浴として酸性タイプのものが望まれて
いる。[Prior art and problems to be solved by the invention] Conventionally, electroless tin plating has been applied to electronic parts etc. from the viewpoint of soldering properties, etc., but in this case, plating of electronic parts etc. is unnecessary. Partial plating is often done by masking the area and plating only the necessary areas. When performing such partial plating, especially when plating electronic components, masking accuracy is strongly required, and various masking agents and masking methods have been developed in response to this, but in general, masking agents are sensitive to alkalinity and If plating is performed in a plating bath, the masking pancreas may peel off, and with the diversification of materials such as electronic parts, the number of materials with poor alkali resistance has increased, so it is difficult to use a plating bath for such partial plating. An acidic type is desired.
従来、酸性の無電解錫めっき浴としては、錫イオンと、
錫を溶解するための酸と、チオ尿素から構成されるが、
錫は両性金属であるという性質から、不均化反応等によ
り金属錫、水酸化錫等の不溶性化合物が経時的に形成さ
れ、沈殿を生成する問題があり、浴の安定性が悪いとい
う欠点を有している。また、従来の酸性無電解錫・銅合
金めっき浴は、同様の問題があり、更にこれら従来浴は
析出膜厚が薄いという問題もある。Conventionally, as an acidic electroless tin plating bath, tin ions and
It is composed of acid for dissolving tin and thiourea,
Due to the nature of tin as an amphoteric metal, insoluble compounds such as metallic tin and tin hydroxide are formed over time due to disproportionation reactions, leading to the formation of precipitates, which has the disadvantage of poor bath stability. have. Furthermore, conventional acidic electroless tin/copper alloy plating baths have similar problems, and furthermore, these conventional baths also have the problem of thin deposited films.
以上の点に鑑み、本出願人は先に、均一で微細な粒子の
錫板出物を与え、かつ良好な析出速度を有する酸性の無
電解錫めっき浴として、置換又は未置換のアルカンスル
ホン酸、ヒドロキシアルカンスルホン酸、ベンゼンスル
ホン酸及びナルタレンスルホン酸から選ばれる１種以上
の有機スルホン酸、これらスルホン酸の２価の錫塩、チ
オ尿素、水溶性ジルコニウム塩を含有してなることを特
徴とする無電解錫めっき浴を提案しく特願昭６３−２１
１８４７号）、また、経時による錫の不溶性化合物の生
成が可及的に防止され、かつ良好な析出速度を有する酸
性の無電解錫めっき浴として、２価の錫イオンと、有機
スルホン酸、有機カルボン酸及びホウフッ酸から選ばれ
る１種以上の酸と、チオ尿素と、過塩素酸及び過塩素酸
化合物から選ばれる１種以上の化合物とを含有してなる
ことを特徴とする無電解錫めっき浴を提案し （特願平
１−３７５３８号）。In view of the above points, the present applicant has previously proposed using substituted or unsubstituted alkanesulfonic acid as an acidic electroless tin plating bath that provides uniform and fine-grained tin platelets and has a good deposition rate. , one or more organic sulfonic acids selected from hydroxyalkanesulfonic acid, benzenesulfonic acid, and naltarenesulfonic acid, divalent tin salts of these sulfonic acids, thiourea, and water-soluble zirconium salts. Patent application 1986-21 requesting to propose an electroless tin plating bath.
No. 1847), and as an acidic electroless tin plating bath that prevents the formation of tin insoluble compounds over time as much as possible and has a good deposition rate, divalent tin ions, organic sulfonic acids, and organic Electroless tin plating characterized by containing one or more acids selected from carboxylic acids and borofluoric acids, thiourea, and one or more compounds selected from perchloric acid and perchloric acid compounds. proposed a bath (patent application No. 1-37538).
しかし、これらの錫めっき浴では厚付けが困難で、めっ
き最大膜厚が約３μｍ程度であった。また、錫・鉛合金
めっき浴も同様な事情にあった。However, with these tin plating baths, it was difficult to thicken the tin plating, and the maximum plating thickness was about 3 μm. A similar situation existed with tin-lead alloy plating baths.
ところが、半田付は性の信頼性を高めるには、めっき膜
厚が６μｍ以上であることが要求され、このため厚付け
の容易な無電解錫めっき浴、錫・鉛合金めっき浴が望ま
れた。However, in order to increase the reliability of soldering, a plating film thickness of 6 μm or more is required, and for this reason, electroless tin plating baths and tin-lead alloy plating baths, which can be easily thickened, were desired. .
〔課題を解決するための手段及び作用〕本発明者らは、
上記目的を達成するため鋭意検討を重ねた結果、２価の
錫イオン又は２価の錫イオンと鉛イオンをリン酸又は縮
合リン酸に溶解し、チオ尿素を添加すると共に、還元剤
として次亜リン酸又は次亜リン酸塩を使用することによ
り、析出速度が高く、しかも厚付けが容易であり、かつ
得られるめっき皮膜も良好であることを知見し、本発明
をなすに至ったものである。[Means and effects for solving the problem] The present inventors,
As a result of intensive studies to achieve the above objective, we dissolved divalent tin ions or divalent tin ions and lead ions in phosphoric acid or condensed phosphoric acid, added thiourea, and added hypochlorite as a reducing agent. It was discovered that by using phosphoric acid or hypophosphite, the precipitation rate is high, it is easy to form a thick layer, and the resulting plating film is also good, and the present invention was made based on this finding. be.
従って、本発明は、２価の錫イオン又はこれに加えて釦
イオンと、チオ尿素と、リン酸又は縮合リン酸と、次亜
リン酸又は次亜リン酸塩とを含有してなる酸性の無電解
錫及び錫・鉛合金めっき浴、並びにこれらの浴を用いて
被めっき物をめっきする無電解錫及び錫・鉛合金めっき
方法を提供する。Therefore, the present invention provides an acidic solution containing divalent tin ions or button ions in addition to divalent tin ions, thiourea, phosphoric acid or condensed phosphoric acid, and hypophosphorous acid or hypophosphites. Provided are electroless tin and tin/lead alloy plating baths, and electroless tin and tin/lead alloy plating methods for plating objects to be plated using these baths.
以下、本発明につき更に詳しく説明する。The present invention will be explained in more detail below.
本発明の錫及び錫・鉛合金めっき浴において、２価の錫
イオンを提供する錫源としては種々選択し得、例えば酸
化錫、塩化錫、硫酸錫、更に有機スルホン酸錫、有機カ
ルボン酸錫、ホウフッ化錫等を挙げることができる。な
お、浴中の２価の錫イオン量は１０〜５０ｇ／Ｒ１特に
１０−４０ｇ／Ｑとすることが好ましい。In the tin and tin/lead alloy plating bath of the present invention, various tin sources can be selected for providing divalent tin ions, such as tin oxide, tin chloride, tin sulfate, tin organic sulfonates, tin organic carboxylates, etc. , tin borofluoride, and the like. The amount of divalent tin ions in the bath is preferably 10 to 50 g/R1, particularly 10 to 40 g/Q.
また、釦イオンとしては、塩化鉛、硫酸鉛、スルホン酸
鉛、ホウフッ化鉛、酸化鉛を用いることができる。これ
らの鉛イオンの量は合金量等に応じて選定し得るが、通
常１〜２０ ｇ ／ Ｑ、特に３〜９ｇ／Ωとすること
ができる。Further, as the button ion, lead chloride, lead sulfate, lead sulfonate, lead borofluoride, and lead oxide can be used. The amount of these lead ions can be selected depending on the amount of alloy, etc., but it can usually be 1 to 20 g/Q, particularly 3 to 9 g/Ω.
更に、本発明浴にはチオ尿素が添加され、チオ尿素の添
加により、錫、錫・鉛合金の析出が可能になる。Furthermore, thiourea is added to the bath of the invention, and the addition of thiourea makes it possible to deposit tin and tin-lead alloys.
なお、チオ尿素の使用量はめっき浴ＩＱ当り３ｏ〜１３
ｏｇ、特ニ５０−１１０ ｇとすることが好ましい。The amount of thiourea used is 3o to 13o per plating bath IQ.
og, preferably 50-110 g.
また、本発明のめっき浴はリン酸又は縮合リン酸を用い
るもので、リン酸、縮合リン酸の使用により、錫、チオ
尿素を安定に溶解することができる。Further, the plating bath of the present invention uses phosphoric acid or condensed phosphoric acid, and by using phosphoric acid or condensed phosphoric acid, tin and thiourea can be stably dissolved.
ここで、縮合リン酸としてはピロリン酸、ポリリン酸等
が使用し得、これらリン酸、縮合リン酸はその１種を単
独で又は２種以上を組み合わせて用いることができるが
、その使用量は５〜６００ｇ ／ Ｑ、特に５０〜３ｏ
ｏｇ／Ｑであることが好ましい。また、金属イオンとの
割合は１：１ｏ〜］：３０、特に１：コ−５〜１：３０
が好ましい。Here, as the condensed phosphoric acid, pyrophosphoric acid, polyphosphoric acid, etc. can be used, and these phosphoric acids and condensed phosphoric acids can be used alone or in combination of two or more types, but the amount used is 5-600g/Q, especially 50-3o
og/Q is preferred. In addition, the ratio with metal ions is 1:1 to ]:30, especially 1:co-5 to 1:30.
is preferred.
なお、上記リン酸、縮合リン酸に加え、本発明では更に
酸として有機スルホン酸、有機カルボン酸、過塩素酸、
ホウフッ酸の１種又は２種以上を併用することができ、
これら酸の使用により素材との密着性を向上させること
ができる。In addition to the above-mentioned phosphoric acid and condensed phosphoric acid, the present invention further uses organic sulfonic acids, organic carboxylic acids, perchloric acids,
One type or two or more types of borofluoric acid can be used in combination,
By using these acids, adhesion to the material can be improved.
この場合、有機スルホン酸としては、アルカンスルホン
酸、ヒドロキシアルカンスルホン酸、ベンゼンスルホン
酸、ナフタレンスルホン酸やこれらの水素原子の一部が
水酸基、ハロゲン原子、アルキル基、カルボキシル基、
ニトロ基、メルカプト基、アミノ基、スルホン酸基など
で置換されたものが使用できる。具体的には、本発明で
好適に使用し得る有機スルホン酸として、メタンスルホ
ン酸、エタンスルホン酸、プロパンスルホン酸、２−プ
ロパンスルホン酸、ブタンスルホン酸、２−ブタンスル
ホン酸、ペンタンスルホン酸、クロルプロパンスルホン
酸、２−ヒドロキシエタン−１−スルホン酸、２−ヒド
ロキシプロパン−１−スルホン酸、２−ヒドロキシブタ
ン−１−スルホン酸、２−ヒドロキシペンタンスルホン
酸、アリルスルホン酸、２−スルホ酢酸、２−又は３−
スルホプロピオン酸、スルホコハク酸、スルホマレイン
酸、スルホフマル酸、ベンゼンスルホン酸、トルエンス
ルホン酸、キシレンスルホン酸、ニトロベンゼンスルホ
ン酸、スルホ安息香酸、スルホサリチル酸、ベンズアル
デヒドスルホン酸、ｐ −フェノールスルホン酸などを
挙げることができる。In this case, the organic sulfonic acid includes alkanesulfonic acid, hydroxyalkanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and some of these hydrogen atoms are hydroxyl groups, halogen atoms, alkyl groups, carboxyl groups,
Those substituted with a nitro group, mercapto group, amino group, sulfonic acid group, etc. can be used. Specifically, organic sulfonic acids that can be suitably used in the present invention include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, 2-propanesulfonic acid, butanesulfonic acid, 2-butanesulfonic acid, pentanesulfonic acid, Chlorpropanesulfonic acid, 2-hydroxyethane-1-sulfonic acid, 2-hydroxypropane-1-sulfonic acid, 2-hydroxybutane-1-sulfonic acid, 2-hydroxypentanesulfonic acid, allylsulfonic acid, 2-sulfoacetic acid , 2- or 3-
Sulfopropionic acid, sulfosuccinic acid, sulfomaleic acid, sulfofumaric acid, benzenesulfonic acid, toluenesulfonic acid, xylene sulfonic acid, nitrobenzenesulfonic acid, sulfobenzoic acid, sulfosalicylic acid, benzaldehyde sulfonic acid, p-phenolsulfonic acid, etc. I can do it.
また有機カルボン酸としては、酒石酸、リンゴ酸、クエ
ン酸、コハク酸、グルコン酸などが使用される。Further, as the organic carboxylic acid, tartaric acid, malic acid, citric acid, succinic acid, gluconic acid, etc. are used.
これら酸の使用量は、特に制限されないが、２０〜３０
０ｇ／Ｑ、特に５０〜１５０ｇ／Ｑとすることが好まし
く、また酸と２価の錫イオンとの割合は１〜１０：１、
特に３〜７：１とすることが好適である。The amount of these acids used is not particularly limited, but 20 to 30
0 g/Q, particularly preferably 50 to 150 g/Q, and the ratio of acid to divalent tin ion is 1 to 10:1,
In particular, a ratio of 3 to 7:1 is preferred.
本発明浴は、上記成分に加え、次亜リン酸又は次亜リン
酸ナトリウム、次亜リン酸カリウム等の次亜リン酸塩を
好ましくは１０〜１５０ ｇ ／ １２、より好ましく
は３０〜７０ ｇ ／ Ｑ添加する。これによりめっき
浴の酸化による劣化を防止する。In addition to the above components, the bath of the present invention preferably contains hypophosphorous acid or a hypophosphite salt such as sodium hypophosphite or potassium hypophosphite in an amount of 10 to 150 g/12, more preferably 30 to 70 g. / Add Q. This prevents deterioration of the plating bath due to oxidation.
なお、本発明のめっき浴は酸性であり、特にｐＨ１，５
以下であることが好ましい。The plating bath of the present invention is acidic, especially at pH 1.5.
It is preferable that it is below.
上述しためっき浴を用いて無電解錫又は錫・鉛合金めっ
きを行う場合、その温度は４０〜７５℃、特に６５・−
７０’Ｃが好ましい。この場合、被めっき物は適宜選定
され、例えば銅、銅合金などの無電解めっきに好適に用
いられる。なお、めっきに際し、必要により撹拌を行う
こともできる。When performing electroless tin or tin-lead alloy plating using the above-mentioned plating bath, the temperature is 40 to 75°C, especially 65°C.
70'C is preferred. In this case, the object to be plated is appropriately selected, and is suitably used for electroless plating of copper, copper alloys, etc., for example. Note that during plating, stirring can be performed if necessary.
次に、実施例及び比較例により本発明を具体的に説明す
るが、本発明は下記の実施例に制限されるものではない
。Next, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
〔実施例１〕 下記組成の無電解錫・鉛合金めっき浴を調製した。[Example 1] An electroless tin-lead alloy plating bath having the following composition was prepared.
ホウフッ化錫（Ｓｎ２＋とじて） ２０ｇ／氾
ホウフッ化鉛（ｐ ｂ”＋とじて） ５０ ｇ
／ Ｑチオ尿素 ８０
ｇ ／ Ｑピロリン酸 ２００
ｇ ／ Ｑ次亜リン酸ナトリウム ５０
ｇ ／ ＱｐＨ０，８
〔比較例１〕
下記組成の無電解錫・鉛合金めっき浴を調製した。Tin borofluoride (Sn2+ combined) 20 g/Lead borofluoride (p b” + combined) 50 g
/ Q Thiourea 80
g/Q pyrophosphoric acid 200
g/Q sodium hypophosphite 50
g/QpH 0.8 [Comparative Example 1] An electroless tin/lead alloy plating bath having the following composition was prepared.
ホウフッ化錫 ２０ ｇ ／ （
ｌホウフッ化釦 ８ｇ／Ｑホウ
フッ酸 ２００ｇ／Ｑ次亜リン酸
ナトリウム ５０ｇ／Ｑチオ尿素
８０ ｇ ／ ＱＰＨ０，１
次に、上記めっき浴を用いて銅板上に温度７０℃でめっ
きを施し、めっき時間と析出膜厚との関係を調へた。結
果を第１図に示す。Tin borofluoride 20 g / (
l Borofluoride button 8g/Q Borofluoric acid 200g/Q Sodium hypophosphite 50g/Q Thiourea
80 g/QPH0,1 Next, a copper plate was plated at a temperature of 70° C. using the above plating bath, and the relationship between the plating time and the deposited film thickness was investigated. The results are shown in Figure 1.
〔実施例２〕 下記組成の無電解錫めっき浴を調製した。[Example 2] An electroless tin plating bath having the following composition was prepared.
ホウフッ化８ ２０ ｇ ／ Ｄ
。Borofluoride 8 20 g/D
.
チオ尿素 ８０ ｇ ／ Ｑ
ピロリン酸 ２００ ｇ ／
Ｑ次亜リン酸ナトリウム ５０ ｇ ／
Ｑｐ）（ｏ、２
〔比較例２〕
下記組成の無電解錫めつき浴を調製した。Thiourea 80g/Q
Pyrophosphoric acid 200g/
Q Sodium hypophosphite 50 g /
Qp) (o, 2 [Comparative Example 2] An electroless tin plating bath having the following composition was prepared.
ホウフッ化錫 ２０ ｇ ／ Ｑ
ホウワラ酸 ２００ ｇ ／
Ｑ次亜リン酸ナトリウム ５０ ｇ ／
ｎＰ）（ｏ、１
次に、上記めっき浴を用いて実施例１と同様にめっきを
行い、めっき時間と析出速度との関係を調べた。結果を
第２図に示す。Tin borofluoride 20 g/Q
Bowaric acid 200 g /
Q Sodium hypophosphite 50 g /
nP) (o, 1) Next, plating was performed in the same manner as in Example 1 using the above plating bath, and the relationship between plating time and precipitation rate was investigated. The results are shown in FIG.
本発明の酸性無電解錫、錫・鉛合金めっき争は析出速度
が大きく、また厚付けが容易であり、本発明浴を用いた
無電解錫、錫・鉛合金めっき方法は効率のよいめっきが
可能なものである。The acidic electroless tin and tin-lead alloy plating method of the present invention has a high deposition rate and can be easily formed thickly, and the electroless tin and tin-lead alloy plating method using the bath of the present invention provides efficient plating. It is possible.
Claims (1)
ン酸と、次亜リン酸又は次亜リン酸塩とを含有してなる
ことを特徴とする酸性の無電解錫めっき浴。 ２．２価の錫イオンと、鉛イオンと、チオ尿素と、リン
酸又は縮合リン酸と、次亜リン酸又は次亜リン酸塩とを
含有してなることを特徴とする酸性の無電解錫・鉛合金
めっき浴。３．請求項１に記載の無電解錫めっき浴に被
めっき物を浸漬して、該被めっき物上に錫めっき膜を形
成する無電解錫・鉛めっき方法。 ４．請求項２に記載の無電解錫合金めっき浴に被めっき
物を浸漬して、該被めっき物上に錫・鉛合金めっき膜を
形成する無電解錫・鉛合金めっき方法。[Scope of Claims] An acidic compound characterized by containing 1.divalent tin ions, thiourea, phosphoric acid or condensed phosphoric acid, and hypophosphorous acid or hypophosphites. Electroless tin plating bath. 2. An acidic electroless product containing divalent tin ions, lead ions, thiourea, phosphoric acid or condensed phosphoric acid, and hypophosphorous acid or hypophosphites. Tin/lead alloy plating bath. 3. An electroless tin/lead plating method comprising immersing an object to be plated in the electroless tin plating bath according to claim 1 to form a tin plating film on the object. 4. An electroless tin/lead alloy plating method comprising immersing an object to be plated in the electroless tin alloy plating bath according to claim 2 to form a tin/lead alloy plating film on the object.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2184488A JP2654715B2 (en) | 1990-07-12 | 1990-07-12 | Electroless tin and tin-lead alloy plating bath and plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2184488A JP2654715B2 (en) | 1990-07-12 | 1990-07-12 | Electroless tin and tin-lead alloy plating bath and plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0472071A true JPH0472071A (en) | 1992-03-06 |
| JP2654715B2 JP2654715B2 (en) | 1997-09-17 |
Family
ID=16154054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2184488A Expired - Lifetime JP2654715B2 (en) | 1990-07-12 | 1990-07-12 | Electroless tin and tin-lead alloy plating bath and plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2654715B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004277814A (en) * | 2003-03-14 | 2004-10-07 | Ishihara Chem Co Ltd | Method for division-preserving electroless tinning bath |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4660814B2 (en) * | 2004-12-22 | 2011-03-30 | 石原薬品株式会社 | Electroless tin plating bath |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51134334A (en) * | 1975-05-06 | 1976-11-20 | Amp Inc | Hot dip coating method for tinnlead alloy |
| JPS54141341A (en) * | 1978-04-26 | 1979-11-02 | Shinko Electric Ind Co | Nonelectrolytic tin plating solution |
| JPS6167770A (en) * | 1984-09-07 | 1986-04-07 | Kizai Kk | Plating method of magnesium and magnesium alloy |
| JPS621122A (en) * | 1985-03-25 | 1987-01-07 | Seiko Instr & Electronics Ltd | Plating bath for producing vertical magnetic recording medium |
| JPH01180986A (en) * | 1988-01-12 | 1989-07-18 | Japan Steel Works Ltd:The | Electroless copper plating method |
-
1990
- 1990-07-12 JP JP2184488A patent/JP2654715B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51134334A (en) * | 1975-05-06 | 1976-11-20 | Amp Inc | Hot dip coating method for tinnlead alloy |
| JPS54141341A (en) * | 1978-04-26 | 1979-11-02 | Shinko Electric Ind Co | Nonelectrolytic tin plating solution |
| JPS6167770A (en) * | 1984-09-07 | 1986-04-07 | Kizai Kk | Plating method of magnesium and magnesium alloy |
| JPS621122A (en) * | 1985-03-25 | 1987-01-07 | Seiko Instr & Electronics Ltd | Plating bath for producing vertical magnetic recording medium |
| JPH01180986A (en) * | 1988-01-12 | 1989-07-18 | Japan Steel Works Ltd:The | Electroless copper plating method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004277814A (en) * | 2003-03-14 | 2004-10-07 | Ishihara Chem Co Ltd | Method for division-preserving electroless tinning bath |
| JP4524773B2 (en) * | 2003-03-14 | 2010-08-18 | 石原薬品株式会社 | Split storage method of electroless tin plating bath |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2654715B2 (en) | 1997-09-17 |
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